Method of preparing powdered cellulose ethers quickly soluble in cold water



Patented Oct. 12, 1943 UNITED. STATES PATENT orrica LULOSE ETHERS QUICKLY SOLUBLE IN COLD WATER Richard w. Swinehart and Albert '1. Maasberg, Midland, Mich, assignora to The Dow Chem ical Company, Midland Mich, a corporation of Michigan No Drawing. Application March 20, 1942,

Serial No. 435,557

ing an improved form of cellulose ethers which are insoluble in hot water and soluble in cold water and particularly to a method of preparing the dried product; However, the resultant ground- 5 Claims. (01. 260-232) material dissolves only extremely slowly in cold water and the method is incapable of practical industrial application.

It is, therefore, an object of the presentinventhe same in a form which dissolves readily in 5 tiontoprovideamethod of preparing cold-watercold water. soluble cellulose ethers in a form more easily dis- Although many cellulose ethers such as methyl solved in cold water than are the fibrous forms cellulose, ethyl cellulose, etc., which are insoluheretofore available. ble in hot water, are ordinarily described as being An additional object is to provide a method 01 soluble in cold .water, it is well. known that it is p par n the a resaid ellu s t rs in a d y. necessary to treat these ethers, which have herepowde ed o m compatible with other dry matetofore been available only in fibrous form, with rials, such as pow y P adh s v s. hot water for from to 30 minutes before they. -etc., to form dry c p s which y be can be satisfactorily dispersed or dissolved in brought into solutionor suspension in cold water cold water. such difilcultly soluble fibrous celby simple mixing, whereby thecellulose ether lulose ethers are herein referred to as cold-waterperforms its 11 and characteristic functmns in soluble cellulose ethers. The indirect procedure the solution o ksusp just referred to for preparing cold-water solu- An additional object is to provide a method of tions of the cold-water-soluble cellulose ethers is preparing the aforesaid cellulose ethers as dry, obviously time-consuming, expensive, and other- 20 free flowing, non-caking powders with an apparwise disadvantageous in many manufacturing ent density greater than that of the forms hereoperations wherein aqueous compositions comtofore available, thus greatly facilitating storage, prising these ethers are made. Thus, it is frehandling and shipping. q y n e sary to pr pare the solution of the An additional object is to provide a method cellulose ether separately from the solution or whereby cold-water-soluble cellulose ethers may suspension of the other ingredients and to then be converted to a form easily dissolved in cold mix the two to form the final composition. The water. necessity of following such a procedure also ob- The foregoing and related objects are readily viously precludes, in a great many instances, the accomplished by forming a wet mixture comprispossibility of preparing mixtures of the-dry coldingxa fibrous cold-water-soluble cellulose ether water-soluble cellulose ethers with other dry and from '72 to 88 per centby weight of water, materials, such as water-soluble dyes and pigmaintaining the mixture at a temperature below ments, and of then preparing thickened aqueous 50 C. until partial colloiding has occurred, 1. e., Solutions r p n i ns therefrom, e pec lly until a translucent mass without visible fibrous since many of the substances which it is desir structure is obtained, drying the partially colable to mix with the dry ether are affected adloided composition and grinding the dried prodversely by contact with hot water. uct. i Various procedures have been tried without The undried colloidal mixture may, depending success in attempting to prepare the cellulose upon the conditions under which colloiding is ethers in a form easily dissolved in cold water. 40 carried out, vary in consistency from a-solid, Thus it has been proposed to grind, shred or friable gel to a translucent, jellylike mass or, in v otherwise subdivide the ethers. to increase the case colloiding is carried too far, to a transparrate of dissolving. However, the fibrous forms j ent gel or even to a liquid sol. of the cellulose ethers are difiicult to grind or Although any cold-water-soluble fibrous cel-- shred and the finely divided material is little, lulose ether may be converted by the method of if any, more easily dissolved in cold water than the present invention to a form easily dissolved the unground material. The fibrous cellulose in cold water without a preliminary hot water ethers, regardless of their state of subdivision, treatment, the description of the invention will, are not easily wetted by cold water, float on the for the sake of simplicity, be limited to its applisurface when added to cold water, and tend to so cation to the preparation of methyl cellulose in form lnto'soft lumps, balls or nodules, which it is such form. a practically impossible to disperse in coldwater. The wet fibrous methyl cellulose may result .It has also been proposed to d y q ous solufrom a manufacturing operation, e. g., from an tions of the cellulose ethers and to then grind operationwherein methyl cellulose is prepared in lgnown manner and washed with hot water to free it from water-soluble impurities, or it may be prepared in any convenient manner, such .as by making a uniform slurry of from 1 to 5 per cent by weight of methyl cellulose in hot water and subsequently removing the excess water, e. g., by pressing or by filtering under vacuum until only the desired proportion of water is retained in the methyl cellulose. Although the methyl cellulose may be treated with hot water in the above or equivalent manner at any temperature above 50 C., the treatment is preferably carried out at above 70 0., since by so doing a more uniform distribution of the water throughout the mass of the methyl cellulose appears to be obtained. The treatment with hot water may be carried out under super-atmospheric pressure if desired. Although the optimum water content of the water-wet methyl cellulose depends to some extent upon the properties of the particular methyl cellulose employed, a methyl cellulose-water composition comprising from 72 to 88 per cent, preferably from '15 to 85 per cent, by weightof water is usually employed. The use of too small a proportion of water will not ordinarily allow the subsequent colloiding, or gel formation, to proceed uniformly throughout the mass, while the use of too large a proportion of water may allow the colloiding to proceed 'so rapidly that it is difllcult to subsequently dry the partially gelled prod-' uct before colloiding has progressed to an undesired degree.

The water-wet fibrous methyl cellulose is cooled to below 50 C., preferably to from 5 'to 23 C. The cooling maybe carried out in any convenientmanner, such as by spreading the methyl cellulose on trays and blowing air over it. Care should be taken that undue evaporation of moisture does not take place during the cooling step, since by such evaporation the water content may be lowered to below that required to give satisfactory control of the subsequent colloiding step, or the evaporation of water from the outer layers of the methyl cellulose maylead to uneven gelling of the mass. The cooling may be carried out in a closed system or the humidity of the cooling air may be adjusted to prevent undue evaporation of water. It is usually prefer able that the cooling take place as rapidly as possible and that the temperature change throughout the mass be as uniform as is consistent with practical considerations. Other obvious ways of cooling the mass while preventing evaporation of undue amounts of water are apparent.

After the mass has cooled sufilciently, it is allowed to age until the desired degree .of gel formation has taken place. Although this usually requires from 5 to 60 minutes, shorter or longer periods may be employed if desired. During the aging period the temperature is maintained sub-' mat of white fibers. As colloiding proceeds the mat becomes slightly grayish in appearance and when the desired degree of gel formation has been reached, little, if any, fibrous structure can beobserved although the mass is translucent.

Further colloiding which is undesirable, converts the mass to a practically transparent gel which is nearly useless for making the product of the present invention.

It has been observed that gel formation may be hastened considerably and a wider range of water content employed by mechanically colloiding the wet methyl cellulose. This mode of operation is described more fully in a concurrently filed, copending application, Serial No. 435,558.

After gel formation has proceeded to the desired degree, themass is dried in any convenient manner, such as by placing it on trays and blowing hot air over it. In case the colloiding step is carried out with the material spread on trays, a stream of hot air may simply be blown over the trays as soon as the desired degree of gel formation has been attained. Drying is carried out as rapidly as convenient and at any desired temperature below about 160 C. The temperature is preferably raised rapidly to to 55 C. to premass is practically transparent.

stantially constant. It should be understood that colloiding probably begins as soon as the temperature has fallen to, or slightly below, 45 to 55 C. and that'it proceeds more rapidly-as the temperature is lowered further. For this reason the time during which the temperature of the .mass is'held substantially constant within the preferred colloiding range will depend, among other factors, upon the amount of colloiding taking place during the cooling just described, 1. e. upon the rate of cooling between 45 or 55 C. and the preferred colloiding range.

The progress of the colloiding step may be observed visually. The mass, before colloiding begins, has the appearance of a fairly compact It is thought that by arresting the colloiding, as previously described, while the mass is still translucent, a gel of sufiicient structural strength is obtained to prevent complete collapse of the gel structure when it is dried and that a relatively porous product is thus obtained. It has been noted that when colloiding is continued until a practically transparent gel is obtained and the gel then dried, a ,homy product is obtained which does not possess the desirable solubility characteristics of the product of the present invention.

The dried product may contain less than 15 per cent, preferably less than 10 per cent, of moisture. easily pulverized, is ground in any of the usual types of pulverizers, and is then ready for use. Although the fineness to which the product is ground is optional, it has been found that a product of 60 to 100 mesh fineness, or finer, is a free-flowing, non-caking powder which dissolves readily when simply stirred with cold water. The individual particles are easily wetted by cold water and sink immediately upon being added to water. 100 cubic centimeters of the powdered methyl cellulose usually weighs between 35 and 45 grams, as compared with the usual weight of from 10 to 15 grams for 100 cubic centimeters of the ordinary fibrous methyl cellulose.

Although, as hereinbefore mentioned, the process of the present invention is applicable to the manufacture of a powder easily dissolved in cold water from any cold-water-soluble cellulose ther,

' suchas canbe made, for example, by alkylating an The dried material, which is friable and mass which is then washed with hot water. The

washed fibrous mass may conveniently serve as a starting material or the present invention.

' It may be mentioned that the process hereindescribed may easily be adapted to continuous operation, since the steps involved are of a type lending themselves particularly to this mode of operation. A uniform product may thus be produced in volume and at low cost.

In a particular example: one part by weight a of fibrous methylceilulose which had a methoxyl content of 30.5 per cent and which when dissolved by the usual method involving a. preliminary treat -ment with hot water formed a 2 per cent by spread on trays and cooled by blowing a stream oi airv over it. The humidity of the air was ad- Justed so that little or no evaporation of water from the methyl cellulose took place during the cooling. Cooling was continued until-the temperature of the wet methyl cellulose reached 18 0. Approximately 20 minutes was consumed .in

cooling the material from 50 C. to 18 C. The cooled wet material was then held at 18 C. for an additional 20'minutes, at the end or which time a stream of air heated to 105 C. was blown over it to dry it. Drying was continued until the moisture in the methyl cellulose had been reduced to per cent byweight. .The dried rnaterlal was. then removed from the trays and ground. The methyl cellulose so obtained was in the form of a-iree-flowing, non-coking powder which weighed 40 grams per 100 cubic centimeters, which sank immediately when thrown into cold water, and which dissolved rapidly upon being stirred with cold water.

stable during storage and when stirred with cold water formed thickened stable solutions and suspensions, respectively, similar in every respect to solutions and suspensions prepared in the best accepted manner using ordinary. fibrous methyl cellulose. A 2 per cent solution prepared by stirring 2 grams or the methyl cellulose with '98 Grams of water at 25 C. had a. viscosity of 3300 centipoises at C. We claim: l. A method or treating -a fibrous cold-watersoluble cellulose ether to improve its rate 01 solution incold water which comprises adiusting the water content of the water-wet fibrous ether at a temperature above 50 C. to a value of from 72' 1o 2. Method according to claim 1, in which the;

cellulose ether is methyl cellulose. I

- 3. A method 01' treating a fibrous cold-watersoluble methyl cellulose to improve its rate of solution in cold water which comprises wetting 15 the ether with hot water at a temperature above 50 C., filtering and removing water from the mass, while still at a temperature-above 50 C., until the moisture content of the same is reduced to a value of from 72 to 88 per cent by weight. 2 cooling the moist mass to a temperature below 50 C. and maintaining it below such temperature until the mass becomes translucent and substantially without visible fibrous structure, then heating the mass to a temperature above 50 C.

to'dry the same to a moisture content below 15 by weight, and grinding the dried prod- C. and methyl cellulose having a methoxyl content of from 23 to 33 per cent, filtering the mass and removing water therefrom, while maintain- 35 1118 the same at a temperature above 0., until the moisture content of the same is reduced to a value of from to per cent by weight, cooling the moist mass to a temperature below 50 C. and

maintaining it below such temperature until the mass becomes translucent and substantially without visible fibrous structure, then air-drying the same at a temperature between 50 C. and C. until the moisture content i reduced to a value below 15 per cent by weight, and grinding the dried product.

5. In a method of preparing a cold-watersoluble methyl cellulose which is readily wettable by and soluble in water, the steps which consist and 88 per cent by weight, at a temperature below 50 0., until gelation has proceeded to the point thatthe fibrous structure of the mass has substantially disappeared, then heating to]; temllerature above 50 C. to arrest further gel formation, and drying the mass.

' RICHARD W. SWINEHART. ALBERT T. MAASBERG. v

in holding a-water-wet mass of fibrous methyl cellulose, having a moisture content between-72 v 

